Compositions containing hydrolyzed vinyl ester homopolymers or vinyl ester/ethylene copolymers and selected fluoroalcohols



United States Patent 3,153,004 COWOSITEUNS CONTAINENG HYDROLYZED VINYLESTER HOMOPOLYWRS OR VINYL ESTER/ETHYLENE (IOPOLYMERS AND Ski- LECTEDFLUOROALCOHOLS William J. Middleton, Wilmington, Del, assignor to E. I.du Pont de Nemours and Company, Wilmington, DeL, a corporation ofDelaware No Drawing. Filed Sept. 29, 1961, Ser. No. 141,593 20 Claims.(Cl. 260--33.4)

This invention relates to, and has as its principal object provision of,novel polymer compositions comprising, as essential ingredients,synthetic polyhydroxy polymers containing vinyl alcohol units andcertain polyhalogenated alcohols.

In many applications of high molecular Weight polymers, such as filmcasting, coating, molding, use as adhesives, etc., solubility in organicsolvents is a desirable property. Solubility at low or moderatetemperatures, e.g., room temperature, is especially desirable in orderto avoid or minimize the degradation of the polymer which often takesplace when solution must be eflected at high temperatures to achieve apractically useful concentration of the polymer in the solvent. Inaddition to fluid solutions, solid or semisolid compositions wherein thepolymer is homogeneously mixed with relatively small amounts of solventserving as plasticizer or physical modifier have great utility inpolymer technology, and

these also require good solubility in the solvent at ordinarytemperature.

Many polyhydroxy polymers sufler from the disadvantages of poorsolubility, or even complete insolubility, in organic solvents and thusare not as broadly useful as they would otherwise be. This isparticularly the case with polyvinyl alcohol and the hydrolyzedolefin/vinyl carboxylate copolymers.

Some polyhydroxy polymers, for example, polyvinyl alcohol, are normallysoluble in Water (although special processes are known whereby polyvinylalcohol is obtained as a material insoluble in and unaffected byboilwhere R is perhalomethyl or an w-ChlOIO- or w-hydroperfluoroalkylradical of l to 4 carbon atoms; R is fluoroperhalomethyl or an w-ChlOIO-or w-hydroperfluoroalkyl radical of 1 to 4 carbon atoms; and A is H, OH,perhalomethyl, phenyl, halophenyl, hydroxyphenyl, CECH, -CECC6H5, oralkoxy of 1 to 2 carbon atoms; and

X IMO-111E011 where X and X are fluorine or chlorine, and A is OH,alkoxy of 1 to 2 carbon atoms, phenyl, halophenyl or hydroxyphenyl.

It will be seen from Formula I and II that the polymer solvents suitablefor use in the compositions of this invention are secondary and tertiarypolyhaloalcohols having a specific structure. Among such alcohols areincluded the gem-diols or -1,1-diols, i.e., the polyketone hydrates(A=OH in Formulas I and II) For reasons of greater accessibility andeffectiveness 1 as solvents, the preferred polyhaloalcohols are thosecoring water).: However, solutions of such water-soluble polymers inorganic solvents are still highly desirable for many uses, for example,in spinning a polymer solution into another liquid medium which does notdissolve, and therefore coagulates, the polymer; in film casting, Wherequick evaporation of the solvent is desired; in extruding plasticizedpolymer/ solvent compositions( solid solutions) to form shaped objects,for example, by injection molding; in the preparation of clear solutionsfree from vinyl carboxylate homopolymer or vinyl carboxylate/ ethylenecopolymer wherein the ratio of vinyl carboxylate units to ethylene unitsis betweenflzS and 50:1, the degree of hydrolysis in said hydrolyzedpolymers and copolymers being at least and a polyhaloalcohol'in whichall halogen atoms are of atomic number 9 to 17, i.e., are fluorineor'chlorine, said polyhaloalcohol having one of the general formulas:

(I) R l y r R \OH responding to formula I and in which R and R arefluoroperhalomethyl groups, i.e., CF CF CI and CFCl and A is H or 0H,especially the latter.

Many of the above-defined secondary or tertiary polyhaloalcohols can beprepared by methods described in the literature or by extensions ofthese published methods. Others are obtainable by methods described incopending patent applications. These include:

(1) The hydrates of the open-chain polyfluloroperhaloandw-hydropolyfluoroperhaloketones, i.e., the compounds of Formula I WhereA is hydroxyl. These gemdiolscan be prepared by the process of US.Patent 2,980,738 or, as described in application Ser. No; 730,266,

filed by D. W. Wiley on April 23, 1958, now Patent No. 3,091,643, by thereaction, in a molar ratio of at least 2:1, of an ester of apolyfluoroperhaloor w-hydropolyfluonoperhaloalkanecarboxylic acid withan alkali metal alkoxide at temperatures below about 0., followed byacidification. This reaction gives the ketones and/or their hydrates,i.e., the gem-diols.

(2) The hydrates and hemiketals of polyfluoroperhalocyclobutan-ones,i.e., the products of Formula II Where A is hydroxy or alkoxy. Thesecompounds can be prepared by the method desoribed in D. C. 'Englands US.Patent 3,039,995 and his application Ser. No. 43,331, filed July 18,1960. This method comprises the hydrolysis by concentrated sulfuric acidof the 1,3,3,4,4-pentafluoro-2,2-dihalo-1-hydrocarbyloxycyclobutanes,i.e., the ethers of the formula and a perfluorovinyl hydrocarbyl ether FC=CFOR. The hydnolysis step yields the polyfluoroperhalocyclobutanonesand/ or their hydrates. The free ketones form hydrates orhemiketalsrapidly and spontaneously by reaction with water or alcohols. l Y i (3)The l-phenyl, l-hydroxyphenyl and l-halophenylperhalocyclobutanols,i.e., the compounds of Formula II Where A is phenyl, hydroxyphenyl orhalophenyl. These 7 compounds can be prepared by the process describedin application Ser. No. 3 2,541, filed by D. C. England on May 31, 1960. In this process a '3,3,4,4-tetrafluoro-2',2-

dihalocyclobutanone is reacted with an aromatic hydrocarbon (e.g.,benzene) in thepresence of conventional :Friedel-Crafts catalysts, orwithphenol orfa halobenzene, in which case no catalyst is necessary.With the 1 more reactive systems the reaction is spontaneous andexothermic. In other cases, a reaction temperature in 'the range of75200 C. is suitable.

(4) The bis-perhaloalkyl (ior w-hydroperhaloalkyl) phenyl-,hydroXyphenyL, or halophenyl carbinols, i.e., the compounds of Formula Iwhere A is phenyl, hydroxyphenyl or halophenyl. These compounds can beprepared by the methods described in application Ser. No. 107,296, filedon May 3, 1961 by D. C. England. In these methods the appropriatepolyhaloalkylketone is condensed with the appropriate aromatic reactantin the presence of the usual Friedel-Crafts catalysts, at moderate vtemperatures in the range of 50150 C.; or the polyhaloalkylke tone isreacted with anarylmagnesium bromide in anhydrous ether, at temperatureswhich maybe as low as 50 C..and generally need not; exceed roomtemperature.

(5) The bis(w-hydroperfluoroalkyl)carbinols, i.e., the compounds ofFormula-I where R and R'Ia're w-hydro- 'periluoroalkyl groups and A ishydrogen. These compounds can be prepared by the process described inUS. Patent 3,022,356, which consists in (a) telomer-izingtetrafluoroethylene and methanol as described in US. Patent 2,558,628;(b) esterifyin'g the primary alcohols present in the reaction mixturewith a carboxylic acid or an hydride; and (c) distilling the-resultingreaction mixture to separate the bis( w-hydroperfiuoroalkyl)carbinolsfrom the esters of the primary alcohols;

For illustrativepurposes, a number of representative specificpolyhaloalcolrols suitable fo'ruse in the compositions of this inventionare listed below by name and formula:

- 1,1,3-trichloro-1,3,3 trifluoro-2-propanolPerfluoro(2-rnethyl-2-propanol) 1,4,4,4tetrachloro-3-trichloromethyl-1,1,2,2-tetrafluoro-1H,9H-hexadecafiuoro-5,S-nonanediol 01% OF J-CF 3-butanol c013 olor orrLo 01:

' 1,3-dichloro-1,1,3,3tetrafluoro-2-pheny1-2-propano12-phenylhexafluoro-2-prop anol Calls ca eor J 1,1,3-trichloro-1,3,3-trifluoro-2-(p-chlorophenyl)-2 pro pafiol CLEO-00F201 6H 1H,7H-3-(p-hydroxyphenyl)dodecafluoro-3-heptano1 CaH4OH H(CF2)2wrinn on 1,3-dichloro-1,1,3,3-tetrafluoro-2-(p-hydroxyphenyl)-2'propanol olrio 1,1-bis (chlorodifluoromethyl) -3-pheny1-2-propyn-1-o1CIFgC "maze-00H;

GIFaC ,H V

I and II are liquids at ordinary temperature.

. defined above.

' ing efiects. Also,

2-methoxyhexafluoro-2-propanol 7 OCHs CF -O-OF;

H 1,3-dichloro-l,l,3,3-tetrafluoro-2-ethoxy-2-propanol QC-2H5o1FtoooF2o1 H 1H,9H-S-methoXyheXadecafiuoro-S-nonanol 0on3 mmh-o-mrsm HPerfluoro( l, l-cyclobutanediol) /OH FzC-C FzCCFz 0H2-chloro-2,3,3,4,4-pentafluoro-1,1-cyclobutanediol ClF o-o l F,00Fz 0H2,2 -dichloro-3,3 ,4,4-tetrafluoro-1,l-cyclobutanediol 0H Fad-0F, OH1-methoxyhexafiuorocyclobutanol OOH:

FzC C V FAD-C F3 OH 2-chloro-2,3,3,4,4-pentafluoro-l-ethoxycyclobutanolre FzC-CFa 0H l phenylhexafluorocyclobutanol CgHs F2O mil-o1 OH-1-(p-chlorophenyl)hexafluorocyclobutanol otnici F,(:o\ F C-(EF, OH 1-(p-hydroxyphenyl) -2,2-diohlorotetrafiuorocyclobutanol OQHAOH o12o-o FJL-JBF on Most of the polyhaloalcohols defined 'by Formulas Others aresolids with relatively low melting points. Such solids, however, aresuitable for use in the compositions of this invention since, at orslightly above their melting point, they dissolve polyhydroxy polymersof the type In some cases, the solutions remain liquid at roomtemperature owing to the melting pointdepressing effect of the solute.In other cases, they solidify to solid solutions, which can bereliquefied readily on warming when a fluid solution is needed.Further-. more, the normally. solid polyhaloalcohols are suitable forthe preparationof solid, homogeneous blends with the polymer, to whichthey impart plasticizing or softensome, normally solidpolyfluoroperhaloketone hydrates (gem-'diols) are capable of formingmore'or less well defined higher hydrates contain- 'ing from about 0.5to about 1.5 miss at additional water. Such higher hydrates are usuallyliquid at room temperature or below and they are suitable for thepurposes of this invention since they permit forming fluid solutions attemperatures lower than the melting point of the water-free gem-diolwithout appreciable decrease in solvent power.

The polyhydroxy polymers with which this invention is concerned are thehydrolysis products of vinyl carboxylate polymers or vinylcarboxylate/ethylene copolymers, in which products at least of theacyloxy groups are hydrolyzed to hydroxyl groups. Polyhydroxy polymersof this kind are well known in the art. They include, first, polyvinylalcohol, this term embracing the hydrolysis products of polyvinylacetate or other polyvinyl carboxylates, e.g., polyvinyl formate orpropionate, which products may be substantially completely hydrolyzed ormay contain minor amounts of residual vinyl ester units. Polyvinylalcohol is usually obtained commercially as the water-soluble product.However, it insoluble and water-resistant state by the specialprocedures described in US. Patents 2,610,359 and 2,610; 360. Both thewatersoluble and the water-insoluble forms of polyvinyl alcohol areentirely suitable for the purposes of this invention. Another group ofpolymers contemplated for use in this invention comprises the hydrolyzedcopolymers of ethylene and vinyl carboxylates described in US. Patent2,386,347. These products, which are at least 80% hydrolyzed, areobtained from copolymers wherein the ratio of vinyl carboxylate units toethylene units is between 1:5 and 50:1. The vinyl,

ester can be that of any monocarboxylic acid, but it is preferably theester of an acid of formula molecular weight, but even polymers of veryhigh molec-' ular Weight, up to 125,000 or even higher, are soluble inthe fluoroalcohols of the type defined above.

The polymer-solvent mixtures of this invention are homogeneous,single-phase compositions. From the standpoint of physicalcharacteristics, they comprise solid compositions in which the polymeris plasticized or otherwise modified with minor amounts of thepolyhaloalcohol, which may be as low as 0.5% by weight of the polymer,i.e., a weight ratio of 0.005 :1; semisolid compositions, in which thepolymer has incorporated therein sufficient amounts of thepolyhaloalcohol to make it readily deformable; highly viscous solutions;and fluid solutions, which can contain as much as 10,000% ofthe-polyhaloalcohol by Weight of the polymer, i.e., a weight ture of twoor more polyhaloalcohols, one of which is readily volatile while theother or others have lower volatility and are retained, at least inpart, within the polymer upon evaporation of the volatile solvent.

It is also within the scope of this invention to use thepolyhaloalcohol. ihadihixturo with minor amounts of' miscible organicliquids' which have little or no solvent action on the polymer. 'Suchcompositions sometimes can be prepared in an advantageous water-- offertechnical advantages, e.g.', they may lend themselves better to theformation of shaped objects by extrusion or casting. Water may also bepresent in minor polyhydroxy polymers and the Water-misciblepolyhaloalcohols, still higher amounts of water can be present, althoughthe advantages of the invention are fully realized only when thepolyhaloalcohol constitutes the major portion of the total solvent.

The compositions can, of course, contain various nonessentialingredients such as resins, waxes, antioxidants, corrosion inhibitors,acid acceptors, ultraviolet light absorbers, fillers and otheradditives. I

The following examples illustrate specific embodiments of the invention.

In Examplesjl -X, which are given in tabular form for the sake ofconciseness, use was made of one or more of the following representative,polyhydroxy polymers:

A. A commercially available polyvinyl alcohol which was an 88%hydrolyzed polyvinyl acetate.

B. A substantially completely hydrolyzed. ethylene/ vinyl acetatecopolymer containing by weight of ethylene units.

C. A substantially completely hydrolyzed ethylcne/ 8 vinyl acetatecopolymerin which the ratio of ethylene units to vinyl acetate units was2.921 (approximately by weight of ethylene units).

D. A yarn made from a substantially completely hydrolyzed ethylene/vinyl acetate copolymer in which the ratio of ethylene units to vinylacetate units was 2.5 :1 (approximately 60% by Weight of ethylene).

The polymer was added to the polyhaloalcohol designated in the tablebelow at a concentration of about 5% by weight. In many cases, solutiontook'place at room temperature in a few minutes. Raising the temperatureto -100" C. was sometimes required to obtain rapid solution. When thiswas done, the polymer generally remained dissolved when the hot solutionwas cooled to room temperature. In some cases, the solution gelled oncooling and there was occasionally partial separation of the polymer,but the polymer redissolved on warming. The solutions were used to formfilms by casting on a support and allowing the solvent to evaporate. Thefilms were coherent, self-supporting when detached from the support,free from undissolved particles, and, in nearly all cases, clear andfree from haze.

The notations shown in the table below have the following meanings:

R.T.=soluble at room temperature.

H.=soluble at 90-100" C.

H., gel.=soluble at 90-100 C., gelled on cooling.

1-1., sep.=soluble at 90, C. some polymer separation on cooling.

N.T.=not tested.

Examples IVl I Polymer Example Solvent A B o D on I CF Ol-(J-OFzOlH.,'sep H.,ge1 R11 R.T.

on i

' 011 II CF3('3CF3%H1O H.,R.T H.,R.T 1-1., sep H.,sep.

031 III ona-o-ona 13., R.T H., H.,sep N.T.

s on W (incl-(Loren or: iiiIIIIIIIIIIIIIIIIIIII ii bi gf fiii:

Examples VII-X Polymer Example Solvent A B o n II CF3CCF3 H., gel H n11RT. 7 I ()H I vrn n orl z-ononornln 11., arr"--. H 11,121 H.,R.T.

, p i on 7 IX. F2o o R.T-- N.T--- N.T N.T.

I V I I. OHJ HzO 7 Fa' C lB 2 i 0013 p p 7 X-.. croniorl-o-oon R.T-'.N.'1- N.T..'.. V 'N.T. V on I 5 A r v,

- tabulated solvent were obtained at the temperature shown.

These solutions were stable and showed no polymer separation onstanding.

Examples IX-XVI Solution Example Solvent Terp XII 100 XIII 100 XIV 100amo CCECCsH I I CFzCl 011 The compositions of this invention are usefulin many ways. Thus, the solid plasticized compositions containing minoramounts of polyhaloalcohol solvent are suitable as molding powders foruse in the fabrication of shaped objects, for example, by molding orextruding into films, rrods, filaments, tubes and other shapes.Solutions of suitably high viscosity can be used as adhesives to jointogethersurfaces such as wood, metals, ceramics, etc. If desired, apartial solution can be made in place just before use by adding to theuntreated polymer just enough polyhaloalcohol solvent to make it sticky,then pressing the sticky mixture between the surfaces to be bonded. Inthis manner, for example, two shaped pieces XVI . of the polymer itselfcan be welded together by moistening one or both with a little of thepolyhaloalcohol solvent and pressing the pieces one against the other.Fluid polymer solutions are suitable for spinning into a nonsolventmedium which coagulates the polymer. Solutions in relatively volatilepolyhaloalcohols are suitable for dry spinning into a hot gaseousmedium, for wire coating or for casting polymer films on porous ornonporous surfaces to achieve various purposes such as protective ordecorative coatings, the fabrication of safety glass interliners, fuelcell liners, etc. These solutions can also be used to impregnate paper,cardboard or textile materials, for example, to obtain calenderedfabrics or adhesive coatings. Further, a preformed object such as amolded article or a film made of the untreated polymer can besurface-treated with a polyhaloalcohol solvent to obtain various effectsby partial or localized solution or etching.

Since obvious modifications and equivalents in the invention will beevident to those skilled in the chemical arts, I propose to be boundsolely by the appended claims.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

' 1. A homogeneous composition of matter of (1) a first componentconsisting of an essentially linear polymer of a molecular weight of3,000l25,000, said polymer being a member of the group consisting ofhydrolyzed vinylcarboxylate homopolyrners and hydrolyzed vinylcarboxylate/ethylene copolymers wherein the ratio of vinyl carboxylalteunits to ethylene units is between 125 and 50:1, the vinyl carb-oxylatebeing a vinyl ester of a carboxylic acid of the formula C,,H COOH,wherein n is an integer from 0 to 3, the degree of hydrolysis in saidpolymer being at least and (2) a second component consisting of apolyhaloalcohol in which all halogen units are of atomic number 9 to 17having one of the general formulae 'R\ /A R OH and t t- X'OC-OH ra l es,

wherein: R is selected from the group consisting of perhalomethyl andw-chloroand w-hydroperfluoroalkyl of up to 4 carbons; R is selected fromthe group consisting of fluoroperhalomethyl and w-chloro-andw-hydroperfluoroalkyl of up to 4 carbons; A is selected from the groupconsisting of hydrogen, hydroxyl, perhalomethyl, phenyl, halophenyl,hydroxyphenyl, -C. ='CH, -CEC-C6H5; and alkoxy of up to 2 carbons; A isselected from the group consisting of hydroxyl, alkoxy of up to 2carbons, phenyl halophenyl and hydroxyphenyl; and X and X are selectedfrom the group consisting of fluorine and chlorine.

2. The composition of claim 1 wherein the first compo nent is polyvinylalcohol.

3. The composition of claim 1 wherein the secondcomponent is 8. Thecomposition of claim 1 wherein the second component is 9. Thecomposition of claim 1 wherein the second com- 10. The composition ofclaim 1 wherein the second 3,153,004; l 1 12 11. The composition ofclaim 1 wherein the second 17. A homogeneous composition of matter of asubcomponent is stantially completely hydrolyzed polyvinyl acetate andCuHs OH CFHFCM mow d-(0min OH 5 (5H 12. The composition of claim 1wherein the second component is H(CF -CHOH(CF H.

13. The composition of claim 1 wherein the second component is 18. Ahomogeneous composition of matter of .a substantially completelyhydrolyzed polyvinyl acetate and CeH4OH 2)r- (C 2)z 14. The compositionof claim 1 wherein the second component is V 19. A homogeneouscomposition of matter of substantially completely hydrolyzed polyvinylacetate and C013 5 010F2OFT-0-0013 15. A homogeneous composition ofmatter of a sub- 20 I stantially completely hydrolyzed polyvinyl acetateand A homogeneous Composltlon matter of a CFC12 'CHOH CF2C1 stantlallycompletely hydrolyzed polyvinyl acetate and 16. A homogeneouscomposition of matter of a substantlally completely hydrolyzed polyvinylacetate and F C I O H Cl 7- OH 25 2 s 4 F: C C g I omol-o-omol I ()H Noreferences cited.

fatent No, 3 153 004 October l3 1964 William J. Middleton It is herebycertified that error appears in the above numbered patent requiringcorrection and that the said Letters Patent should read as correctedbelow.

Column 10, lines 18 to 21, the formula should appear as shown belowinstead of as in the patent:

same column 10, claims 3 and 4, after the structural formulae e'achoccurrence insert --,R and R being fluoroperhalomethyl groups.

Signed and sealed this 2nd day of February 1965,

(SEAL) Attest:

EDWARD J, BRENNER Attesting Officer

1. A HOMOGENEOUS COMPOSITION OF MATTER OF (1) A FIRST COMPONENTCONSISTING OF AN ESSENTIALLY LINEAR POLYMER OF A MOLECULAR WEIGHT OF3,000-125,000 SAID POLYMER BEING A MEMBER OF THE GROUP CONSISTING OFHYDROLYZED VINYL CARBOXYLATE HOMOPOLYMERS AND HYDROLYZED VINYLCARBOXYLATE/ETHYLENE COPOLYMERS WHEREIN THE RATIO OF VINYL CARBOXYLATEUNITS TO ETHYLENE UNITS IS BETWEEN 1:5 AND 50:1, THE VINYL CARBOXYLATEBEING A VINYL ESTER OF A CARBOXYLIC ACID OF THE FORMULA CNH2N+1COOH,WHEREIN N IS AN INTEGER FROM 0 TO 3, THE DEGREE OF HYDROLYSIS IN SAIDPOLYMER BEING AT LEAST 80%, AND (2) A SECOND COMPONENT CONSISTING OF APOLYHALOALCOHOL IN WHICH ALL HALOGEN UNITS ARE OF ATOMIC NUMBER 9 TO 17HAVING ONE OF THE GENERAL FORMULA